Polymorphic Crystalline Structure Research Articles

Polymorphic Crystalline Structure and Crystal Morphology of Enantiomeric Poly(lactic acid) Blends Tailored by a Self-Assemblable Aryl Amide Nucleator

Stereocomplex (SC) crystallization has been an effective method to improve the heat resistance of poly(lactic acid) (PLA). However, the preparation of SC-type PLA material is still a challenge because SC crystallization is much less prevailing than homocrystallization in the high-molecular-weight (HMW) poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends. In this study, we have successfully promoted SC formation and controlled crystal morphology of a HMW PLLA/PDLA blend by using a self-assemblable aryl amide nucleator, N,N′,N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (BTCA). Crystallization kinetics, polymorphic crystalline structure, crystal morphology and superstructure of BTCA-nucleated PLLA/PDLA blends were investigated. During the nonisothermal melt crystallization and isothermal crystallization at different temperatures (80–170 °C), the crystallization rate of PLLA/PDLA blend is significantly promoted and the fraction of SCs is enhanced with incorporating small amount of BTCA. SCs a...

Promoted Stereocomplex Crystallization in Supramolecular Stereoblock Copolymers of Enantiomeric Poly(Lactic Acid)s

Telechelic and 3-arm star-shaped poly(l-lactic acid)s (PLLAs) and poly(d-lactic acid)s (PDLAs) end-functionalized by 2-ureido-4[1H]-pyrimidione (UPy) self-complementary quadruple hydrogen-bonding motifs were synthesized by terminally modifying the corresponding hydroxyl-terminated polymers. The PLLA/PDLA stereoblock supramolecular polymers (sb-SMPs) with linear and branched architectures were further prepared by mixing the UPy end-functionalized telechelic, 3-arm star-shaped PLLA and PDLA through the dimerization of UPy groups, as verified by viscometry. Crystallization kinetics, polymorphic crystalline structure, and lamellae morphology of the PLLA/PDLA sb-SMPs were investigated and compared with the corresponding blends without UPy end functionalities. Compared to the PLLA/PDLA blends, the sb-SMPs exhibit higher crystallization rate and prefer to crystallizing into the high-melting-point stereocomplex (sc), rather than the low-melting-point homocrystallite in both the nonisothermal and isothermal crysta...

Crystallization behavior and polymorphism of poly(1,4‐butylene adipate): Effect of anhydrous orotic acid as nucleating agent

ABSTRACTThe effect of anhydrous orotic acid (OA), as a biocompatible nucleating agent (NA), on the non‐isothermal and isothermal crystallization behaviors, polymorphic crystalline structure and phase transition of poly(1,4‐butylene adipate) (PBA) was investigated. It is found that the OA increased the crystallization temperature of the PBA in the non‐isothermal crystallization process and decreased the crystallization time of the PBA in the isothermal crystallization process. Meanwhile, the spherulite size decreased and spherulite density increased for the PBA. The OA favored the formation of the PBA α‐form crystal, compared to the neat PBA. In addition, upon incorporation of the OA, the β‐to‐α phase transition rate was enhanced significantly. Mechanisms for the preferential formation of the PBA α‐form crystal and the accelerated phase transition have also been proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 42957.

Modulated crystallization behavior, polymorphic crystalline structure and enzymatic degradation of poly(butylene adipate): Effects of layered metal phosphonate

Layered metal phosphonate, zinc phenylphosphonate (PPZn) was synthesized and used as a model benign nucleating agent for poly(butylene adipate) (PBA) to manipulate the crystallization behavior, polymorphic crystalline structure and biodegradation of PBA. Upon incorporation of PPZn, the crystallization temperature (Tc) and crystallinity of PBA increased. Meanwhile, the crystallization rate and spherulite density of PBA increased in the presence of PPZn, indicating that PPZn has an effective nucleating effect for PBA. PPZn is favorable for the formation of the PBA α-modification. Furthermore, PPZn would speed up highly the phase transition of PBA from the β- to α-one. PPZn significantly suppressed the biodegradation of PBA. Mechanisms for nucleating, preferential formation of the α-modification, accelerated phase transition and decreased degradation rate of PBA in the presence of PPZn have also been proposed. It is considered that layered metal phosphonate material is a new type of benign filler for controlling the polymorphic crystalline structure and biodegradation rate of the polymer, which is expected to further modify the property of the polymer and might widen the applications of biodegradable materials in the environmental and biomedical fields.

Preferential Stereocomplex Crystallization in Enantiomeric Blends of Cellulose Acetate-g-Poly(lactic acid)s with Comblike Topology.

Although stereocomplex (sc) crystallization is highly effective for improving the thermal resistance of poly(lactic acid) (PLA), it is much less predominant than homocrystallization in high-molecular-weight (HMW) poly(l-lactic acid)/ poly(d-lactic acid) (PLLA/PDLA) racemic blends. In this contribution, the sc crystallization of HMW PLLA/PDLA racemic blends was facilitated by using comblike PLAs with cellulose acetate as the backbone. Competing crystallization kinetics, polymorphic crystalline structure, and structural transition of comblike PLLA/PDLA blends with a wide range of MWs were investigated and compared with the corresponding linear/comblike and linear blends. The HMW comblike blend is preferentially crystallized in sc polymorphs and exhibits a faster crystallization rate than does the corresponding linear blend. The sc crystallites are predominantly formed in nonisothermal cold crystallization and isothermal crystallization at temperatures above 120 °C for the comblike blends. Except for the facilitated sc formation in primary crystallization, synchrotron radiation WAXD analysis indicates that the presence of a comblike component also facilitates the transition or recrystallization from homocrystallite (hc) to sc crystallite upon heating. Preferential sc formation of comblike blends is probably attributable to the favorable interdigitation between enantiomeric branches and the increased mobility of polymer segments. After crystallization under the same temperature, the comblike blends, which mainly contain sc crystallites, show smaller long periods and thinner crystalline lamellae than do the corresponding PLLA with homocrystalline structures.

Effects of Cyanuric Acid on Crystallization Behavior, Polymorphism, and Phase Transition of Poly(butylene adipate)

Effects of cyanuric acid (CA) on the isothermal and nonisothermal crystallization, morphology, polymorphic crystalline structure, and phase transition on PBA have been investigated systematically by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) spectroscopy. The nonisothermal crystallization temperature increased upon addition of CA. The crystallization kinetics of isothermal crystallization was quantitatively analyzed. CA is an effective nucleating agent for the enhanced nucleation density and decreased spherulite size of PBA. Addition of CA was favorable for the formation of PBA α modification and accelerated the phase transition from the β modification to the α modification. The mechanisms of nucleation, preferential formation of PBA α modification, and accelerated phase transition have also been proposed.

Effect of the talc filler on structural, water vapor barrier and mechanical properties of poly(lactic acid) composites

Abstract Poly(lactic acid) (PLA) based composite films with different content of talc (5–15 wt%) were prepared by the solvent casting method. The effect of talc on morphological, structural, thermal, barrier and mechanical properties of neat PLA was investigated. The PLA/talc composites revealed a polymorphic crystalline structure, as demonstrated by X-ray diffraction (XRD) study and differential scanning calorimetry (DSC) analysis. The PLA/talc composites also exhibited significantly improved barrier properties (up to 55% compared to neat PLA), as shown by water vapor permeability (WVP) tests. The puncture measurements showed improved mechanical properties at lower content of talc (up to 5 wt%), and increased brittleness of the PLA/talc composite films at higher talc concentrations.

Competitive stereocomplexation, homocrystallization, and polymorphic crystalline transition in poly(L-lactic acid)/poly(D-lactic acid) racemic blends: molecular weight effects.

Competitive crystallization kinetics, polymorphic crystalline structure, and transition of poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends with a wide range of molecular weights (MWs) were symmetrically investigated. Stereocomplex (sc) crystallites are exclusively formed in the low-MW racemic blends. However, stereocomplexation is remarkably depressed, and homocrystallization becomes prevailing with increasing MWs of PLLA and PDLA. Suppressed stereocomplexation in high-MW (HMW) racemic blends is proposed to be due to the low chain diffusion ability and restricted intermolecular crystal nucleation/growth. Equilibrium melting point of sc crystallites first increases and then decreases as MW increases. Crystallinity and relative fraction of sc crystallites in racemic blends enhance with crystallization temperature (Tc), and the sc crystallites are merely formed at Tc > 170 °C because of their higher thermodynamic stability. In situ wide-angle X-ray diffraction (WAXD) analysis reveals that the stereocomplexation and homocrystallization are successive rather than completely simultaneous, and the stereocomplexation is preceding homocrystallization in isothermal crystallization of HMW racemic blends. Both initial crystalline structure of homocrystallites (hc) and MW influence the heating-induced hc-to-sc transition of HMW racemic blend drastically; the hc-to-sc transition becomes easier with decreasing Tc and MW. After crystallization at the same temperature, sc crystallites show smaller long period than their hc counterparts.

All-water-based electron-beam lithography using silk as a resist

Traditional nanofabrication techniques often require complex lithographic steps and the use of toxic chemicals. To move from the laboratory scale to large scales, nanofabrication should be carried out using alternative procedures that are simple, inexpensive and use non-toxic solvents. Recent efforts have focused on nanoimprinting and the use of organic resists (such as quantum dot-polymer hybrids, DNA and poly(ethylene glycol)), which still require, for the most part, noxious chemicals for processing. Significant advances have been achieved using 'green' resists that can be developed with water, but so far these approaches have suffered from low electron sensitivity, line edge roughness and scalability constraints. Here, we present the use of silk as a natural and biofunctional resist for electron-beam lithography. The process is entirely water-based, starting with the silk aqueous solution and ending with simple development of the exposed silk film in water. Because of its polymorphic crystalline structure, silk can be used either as a positive or negative resist through interactions with an electron beam. Moreover, silk can be easily modified, thereby enabling a variety of 'functional resists', including biologically active versions. As a proof of principle of the viability of all-water-based silk electron-beam lithography (EBL), we fabricate nanoscale photonic lattices using both neat silk and silk doped with quantum dots, green fluorescent proteins (GFPs) or horseradish peroxidase (HRP).

Efficient extraction of carboxylated spherical cellulose nanocrystals with narrow distribution through hydrolysis of lyocell fibers by using ammonium persulfate as an oxidant

An efficient and low-cost approach to prepare spherical cellulose nanocrystals (SCNCs) is presented through chemical hydrolysis of lyocell fibers in an ammonium persulfate (APS) solution. The as-prepared cellulose nanoparticles were characterized by scanning electron microscopy, atomic force microscopy, laser light scattering particle analysis, wide angle X-ray diffraction, Fourier transform infrared spectrometry and thermal gravimetric analysis. Effects of hydrolysis conditions, such as reaction time and temperature, and APS concentration on the morphology, microstructure, and thermal stability of cellulose nanoparticles are discussed. Moreover, it is found that under mild reaction conditions, cellulose nanoparticles are spherical particles with a narrow diameter distribution, and have a cellulose II polymorphic crystalline structure with surface carboxyl groups. The optimal hydrolysis time was found to be around 16 h for hydrolysis at 80 °C with a 1 M APS aqueous solution.

Raman spectroscopy of visible-light photocatalyst – Nitrogen-doped titanium dioxide generated by irradiation with electron beam

A promising material in medicine, optoelectronics, catalysis and photophysics, nitrogen-doped titanium dioxide, is investigated by means of vibrational spectroscopies: Raman and UV–Vis. The synthesis of N-doped TiO2 has been accomplished by oxidizing or reducing process either through chemical doping, and calcination or chemical doping enhanced by electron beam irradiation (EB). When ionizing radiation interacts with the polymorphic crystalline structure of TiO2 mixed with N-dopants (urea) active species such as free radicals are produced, thereby initiating chemical reactions that result in N-doping of the crystalline structure of TiO2. We have compared efficiency of doping by calcination and EB using Raman spectroscopy.

Effects of Crystallization Temperature of Poly(vinylidene fluoride) on Crystal Modification and Phase Transition of Poly(butylene adipate) in Their Blends: A Novel Approach for Polymorphic Control

Effects of the isothermal crystallization temperatures of poly(vinylidene fluoride), T(IC,PVDF), on polymorphic crystalline structure, phase transition, fractional crystallization, and enzymatic degradation of poly(butylene adipate) (PBA) in crystalline/crystalline blends have been investigated. The crystal modifications of PBA can be regulated by T(IC,PVDF). Lower T(IC,PVDF) (e.g., 80 °C) facilitates the formation of PBA α crystals in both the isothermal and nonisothermal melt crystallizations and also favors the β-to-α phase transition of PBA upon annealing at elevated temperatures. This might be attributable to the decreased equilibrium melting temperature of PBA when T(IC,PVDF) is decreased. Higher T(IC,PVDF) is favorable for the fractional crystallization of PBA, which tends to segregate in the interlamellar regions of the PVDF matrix under these conditions. PBA shows faster enzymatic degradation in the blends with a lower T(IC,PVDF) than those with a higher T(IC,PVDF), attributable to the preferential formation of α crystals at a lower T(IC,PVDF). This study provides a new method to control the crystal modification and physical properties of polymorphic polymers in their blend systems.

Fractionated crystallization, polymorphic crystalline structure, and spherulite morphology of poly(butylene adipate) in its miscible blend with poly(butylene succinate)

It has been investigated the effects of poly(butylene succinate) (PBS) component on the fractionated crystallization, crystalline structure, and spherulite morphology of polymorphic poly(butylene adipate) (PBA) with melting temperature lower than that of PBS in their miscible binary blends. Fractionated crystallization of the PBA component occurs upon blending with PBS depending on the content and crystallization temperature of the PBS component. It is probably related to the distribution of PBA in the PBS matrix. The PBS component suppresses the crystallization of PBA, due to the physical confinement effect of PBS on the PBA component. PBS is favorable for the formation of the PBA α-crystal in the PBS/PBA blends with C PBS ≤ 70%, suggesting that the polymorphism of PBA can be regulated by PBS. The morphology observation reveals that the spherulite growth direction of PBA is controlled by that of PBS. Furthermore, the morphology of PBA is also manipulated by that of PBS rather than the crystallization temperature. The possible mechanism of morphology generation of PBA controlled by PBS has been proposed. The PBS/PBA blend system is an ideal system to study not only on the polymorphism regulation but also on morphology control of biodegradable polymorphic material by polymer blending without losing the biodegradability.

Micelles of PAAm-b-PEO-b-PAAm Triblock Copolymers and Their Binding with Prednisolon

The IntraPC forming asymmetric PAAm-b-PEO-b-PAAm triblock copolymers (TBCs) composed of poly(ethylene oxide) (M v = 6 · 103 and 1.4 · 104) and polyacrylamide of a variable chain length form “hairy-type” micelles in water and “flower-like” micelles at the addition of EtOH > 40 vol %. The specific micellization is developed in TBC aqueous/ethanol solutions (EtOH content < 30 vol %) at the PS introduction. It is caused by the binding of PS with TBC micelles due to hydrogen bonds and hydrophobic interactions. The amorphous structure of TBCs and polymorphic crystalline structures of PS are found. The products of the interaction of TBC and PS contain highly ordered crystalline structures of the drug. But it is possible to avoid the drug crystallization at low PS contents.

Temperature‐dependent polymorphic crystalline structure and melting behavior of poly(butylene adipate) investigated by time‐resolved FTIR spectroscopy

AbstractThe polymorphic crystalline structure and melting behavior of biodegradable poly(butylene adipate) (PBA) samples melt‐crystallized at different crystallization temperatures were studied by differential scanning calorimetry (DSC) and fourier transform infrared (FTIR) spectroscopy. The crystalline structure and melting behavior of PBA were found to be greatly dependent on the crystallization temperature. By comparison of the FTIR spectra and the corresponding second derivatives between the α‐ and β‐crystal of PBA, the spectral differences were identified for the IR bands appeared at 1485, 1271, 1183, and 930 cm−1 and the possible reasons were presented. Especially, the 930 cm−1 band was found to be a characteristic band for the β‐crystal. Combining the DSC data with the analysis of normalized intensity changes of several main IR bands during the melting process, the melting behaviors of the α‐ and β‐crystal were clarified in detail. It is demonstrated by the in situ IR measurement that the β‐crystalline phase would transform into the α‐crystalline phase during the melting process, and the solid–solid phase transition from the β‐ to α‐crystal was well elucidated by comparing the intensity changes of the 1170 and 930 cm−1 bands. The dependence of the β‐ to α‐crystal phase transition on the heating rate was revealed by monitoring the intensity ratio of the 909 and 930 cm−1 band. It was suggested that at the heating rate of 0.5 or 1 °C/min, the percent amount of the transformed α‐crystal from the β‐crystal was much higher than that at the higher heating rate. The β‐crystal transforms into the α‐crystal incompletely at the higher heating rate because of the less time available for the phase transition. In addition, the β‐ to α‐crystal phase transition was further confirmed by the IR band shifts during the melting process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1997–2007, 2009

Organic Supernanostructures Self-Assembled via Solution Process for Explosive Detection

Three different polymorphic crystalline structures, including microbelts and flowerlike supernanostructures, were obtained via a simple solution process by utilizing different solvents from an oligoarene derivative. Explosive chemosensors based on these self-assembled organic crystalline nanostructures were successfully fabricated. The differences in the structures on the microscopic level and in the film morphologies led to dramatic enhancements of the explosive detection speed. With the evolution of structures from the netted 1D microbelts to the flowerlike supernanostructures, the detection speed of the chemosensors for DNT and TNT was improved by more than 700 times. Our discovery demonstrates that the morphology control through self-assembly provides a new platform to utilize organic crystalline microstructures for chemosensors, optoelectronics, biosensors and bioelectronics, and so forth.

Facile synthesis of spherical cellulose nanoparticles

A practical procedure for synthesizing cellulose nanospheres with sizes ranging from 60 to over 570 nm was developed. This methodology provides a near linear relationship between cellulose nanoparticle size and treatment time. The hydrolyzed nanocelluloses are predominantly cellulose II polymorphic crystalline structure and relatively uniform in particle size.

Changes in Lipid Status and Glass Properties in Cotyledons of Developing Sunflower Seeds

Biochemical events involved in the acquisition of germinability and storability during orthodox seed development are well documented; however, the roles played by the physical organization of lipids and water are poorly characterized. The aim of this work was to determine, using a thermodynamic approach, whether changes in thermal properties of lipid reserves, and intracellular glasses might play a role in sunflower (Helianthus annuus L.) seed development. Triacyglycerols (TAGs) accumulated in cotyledons until the end of seed filling, which occurred 42 days after anthesis (DAA). Further seed development, leading to mature seed at 58 DAA, was mainly associated with an enlargement of lipid bodies without significant changes either in the lipid content or in their composition. When cooled to -100 degrees C, lipid reserves from cotyledons of mature seeds displayed alpha and beta' polymorphic crystalline structures; however, the ability to form alpha crystals, which was an indicator of lipid purity, progressively appeared during seed development. Characteristics of lipid melting confirmed that seed maturation drying was associated with changes in TAG physical organization. Cotyledon development was associated with an increase in the temperature of glass to rubber transition (Tg), thus suggesting a decrease in molecular mobility during maturation drying. This phenomenon was concomitant with an increase in raffinose content. Our results demonstrate that physical characteristics of lipid reserves and glasses of sunflower cotyledons are developmentally regulated and might play a role in acquisition of seed germinability and storability.

Modified genetic algorithm to model crystal structures. II. Determination of a polymorphic structure of benzene using enthalpy minimization

The Modified Genetic Algorithm scheme, presented in Paper I to model crystal structures in organic compounds (MGAC), is applied here to test its performance in the determination of a polymorphic crystalline structure of benzene that has been observed at 25 Kbar. This polymorph, named here benzene II, is not a global minimum of the energy or even close to any of the local minimum determined using the energy evolution of benzene structures described in the previous paper. The benzene II structure corresponds to an enthalpy minimum. This paper shows that it is possible to use the MGAC procedure, modified to use the minimization of the enthalpy instead of the energy in the GA (Genetic Algorithm) selection process, to find this high pressure structure of benzene.

Polymorphic crystalline forms of 8OCB

For most alkoxycyanobiphenyls (3OCB, 5OCB, 6OCB, 7OCB and 9OCB) it has been observed that slow or delayed cooling gave rise to a lower melting crystalline polymorphic form which then slowly converted into the higher melting stable crystalline structure. Although under slow evaporation from a solvent, polymorphic crystalline structures were observed also for 8OCB, a polymorphism on cooling like that in other nOCBs has not previously been reported. We have now observed that 8OCB also shows polymorphism, which brings it into line with the other homologues. On keeping the material between 35 and 38 °C after it was cooled from above the melting point of the stable crystal form (55 °C), regular platelets grow usually from one point and fill the whole sample. The texture is stable for weeks at room temperature. Upon heating it shows a melting point at 50 °C, i.e. 5 degrees below the stable crystalline melting point. It is interesting that all platelets are non-symmetric and have the same handedness.